Evaluation for the curing characteristics of phenolic molding compounds by rockwell hardness test at an elevated temperature

Rockwell hardness measurement at an elevated temperature has been proposed as an evaluation method for the curing characteristics of thermosetting molding compounds. This method is convenient and has a high accuracy over a wide range of curing, Using a cone indenter, the following advantages are brought about: a good correspondence with acetone extraction test, in showing the degree of cure of the internal part of a molding rather than that of the skin layer, and a higher sensitivity in measuring higher degrees of cure. On examining curing behavior of commercial phenolic molding compounds by this method, an inflection point was observed on a plot of the hardness vs log curing time. This critical point has been called “the minimum cure time”, beyond which the molding exhibits good physical properties.     

The electrocatalytic activities of the Pd-doped MnO2 for the chlorine evolution reaction

The anodic evolution of chlorine on the massive β-MnO₂ doped with various amounts of Pd was investigated in acidic chloride solution. A second-order relation was found between the rate of the chlorine evolution reaction and the number of active Pd sites at the electrode surface. And it was confirmed that, in the relatively low doped electrodes, the active sites are more effectively dispersed on the surface with microscopic homogeneity. From the activation energies, it was also suggested that the reaction mechanism on the MnO₂ doped with relatively small amounts of Pd is somewhat different from that on the pure PdO electrode.     

Structural Modulations in Monoclinic Tricalcium Silicate Solid Solutions Doped with Zinc Oxide, M(I), M(II), and M(III)

Structural modulations in solid solutions of C₃S doped with various amounts of ZnO were investigated via the selected-area electron diffraction method. Three monoclinic modifications (M(I), M(II), and M(III)) were identified in the solid solutions. The modifications had pseudohexagonal subcells that were modulated to form supercells. Coordinates of the reflections attributable to the supercells could be expressed by the following linear combinations of vectors of the reciprocal lattices: m₁(−2 a */5.4 + 2 b */5.4 − 7 c */5.4) for M(I), m₂(− a */5 + b */5 − c *) for M(II), and m₃(− a */6 + b */6 + 7 c */6) for M(III), m₁ and m₂=±1 and ±2, and m₃=±1, ±2, and ± 3. All the monoclinic modifications possessed structural modulations of a one-dimensional type. The modulation waves could be detected as wavy contrasts by high-resolution transmission electron microscopy.     

Iodine reaction of vinyl acetate/vinyl propionate copolymers. III. Iodine affinities of the radically polymerized copolymers and the copolymers derived from partially saponified polyvinyl acetate

The minimum sequence lengths (n_c) of vinyl acetate (VAc) units necessary to form a colored iodine complex were determined to be 4 and 17 for radically polymerized VAc/vinyl propionate (VPr) and VAc/isopropenyl acetate (IPAc) copolymers, respectively. The iodine affinities (I/VAc) of VAc/VPr copolymers (SP-series) obtained by propionylation of partially saponified polyvinyl acetate (PVAc) were remarkably affected by the saponification conditions. An increase of the water content in acetone/water mixture as saponification solvent brought about a decrease of the iodine affinities of the SP-series. The dependence of the iodine affinity on the saponification of monomer units in the SP-series was compared with that in the radically polymerized VAc/VPr copolymers by taking the sequence probability as the measure of monomer unit distribution. The results strongly supported an occurence of the slide fastener reaction at high degrees of saponification, which was well-known in the saponification of PVAc. Furthermore, it was found that the saponification mode of PVAc at low degrees of saponification was influenced uniquely by the water content in saponification solvents and the saponification temperature.     

Diffusion/adsorption model of cellulose dyeing. II. Ordinary cellulose–direct dye system

The diffusion and adsorption of C.I. Direct Yellow 12 and Blue 15 in water-swollen ordinary cellophane sheets were examined at various ionic strengths. The concentration dependence of apparent diffusion coefficients, D_c, for these dyes was obtained from the diffusion profiles in the substrate, which were measured by the use of the cylindrical film roll method. The decrease of apparent porosity with an increase in the amounts of adsorption was observed. To explain the diffusion/adsorption behaviors of these systems, a variable porosity model was proposed and was applied to analyze the concentration dependence of D_c's. The diffusion/adsorption behaviors of these dyes could be quantitatively described by this model at relatively low ionic strengths. At higher ionic strengths and/or lower values of C, i.e., at the large values of C_im/C_m, where the C's are the concentrations of immobilized (suffix im) and mobile (suffix m) species, it needed to introduce the concept of dynamic equilibria which occurred simultaneously with diffusion but deviated from the true equiliblia measured by the adsorption experiments.     

Prediction of the biologically active sites in eclosion hormone from the silkworm, Bombyx mori

The structure-activity relationship of eclosion hormone from the silkworm, Bombyx mori, was analyzed. First, the probable active residues in silkworm eclosion hormone and also tobacco hornworm eclosion hormone were predicted by the average distance map method. To examine the contributions of those residues to the activity of silkworm eclosion hormone, Gly-substituted mutants for those predicted residues were produced by site-directed mutagenesis and their activities were evaluated by a bioassay. Finally, Glu12, Met24 and Phe25 were estimated to be the crucial residues for the eclosion hormone activity. The possibility of the development of a blocker of an eclosion hormone receptor on the basis of the present work is also discussed.      

Reaction and diffusion of reactive disperse dye in nylon 6

The diffusion of a reactive disperse dye with a vinylsulfonyl group accompanied by simultaneous reaction with the amino end groups in nylon 6 was examined by the method of cylindrical film roll at 70°C and pH 2.2–8.0. The experimental diffusion profiles of the active and fixed species of the dye in nylon 6 were confirmed to be described by the diffusion equation accompanied by the chemical reaction with substrate taking the limited amount of the end groups into account, where the active species of dye were assumed to react only with the free base of amino end groups. The completion of the reaction with the amino end groups was observed in the first layer from the surface at pH 6.0–8.0. The value of diffusion coefficient was constant (8.0 × 10^?10 cm²/s) at all the pH's. The product of the second-order rate constant, k₂, of reaction of the dye and the dissociation constant, K_a, of the amino end groups was constant (k₂K_a = 4.0 × 10^?9 s^?1) at pH 2.2–8.0. The k₂ values of the reaction with various substrates for vinylsulfonyl and monochlorotriazinyl-reactive dyes were compared and the practical dyeing conditions were discussed.     

Effect of reaction kinetics of polymer electrolyte on the ion‐conductive behavior for poly(oligo oxyethylene methacrylate)–LiTFSI mixtures

The effect of the reaction kinetics on the ionic conductivity for a comblike‐type polyether (MEO) electrolyte with lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) was characterized by DSC, complex impedance measurements, and ¹H pulse NMR spectroscopy. The ionic conductivity of these electrolytes was affected by the reaction condition of the methacrylate monomer and revealed by the glass transition temperature (T_g), spin–spin relaxation time (T₂), steric effects of the terminal groups, and the number of charge carriers indicated by the VTF kinetic parameter. In this system, the electrolytes prepared by the reaction heating rate of 10°C/min of MEO–H and 15°C/min of MEO–CH₃ showed maximum ionic conductivity, σ_i, two to three times higher in magnitude than that of the σ_i of the others at room temperature. As experimental results, the reaction kinetic rate affected the degree of conversion, the ionic conductivity, and the relaxation behaviors of polyether electrolytes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2149–2156, 2003     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.